Azo compounds of the thiophanthraquinone series



Patented July 10, 1951 AZO COMPOUNDS OF THE THIOPHANTHRA- QUINONE SERIES Herman E. Schroeder and Lorraine A. Ringrose, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application June 17, 1949, Serial No. 99,876

Claims.

This invention relates to the preparation of new dyes and dye intermediates of the thiophanthraquinone series, and more particularly to new azo-biphenyl-carbonylaminothiophanthraquinones of the general formula:

2 phanthraquinone vat dyes which are 4,4"'-substituted azobiphenyl compounds carrying at least one thiophanthraquinoneiminocarbonyl group.

The compounds of the present invention are prepared by condensing one mol of an aminothioin which one B stands for a thiophanthraquinone radical and the second R for an anthraquinone radical or a second thiophanthraquinone radical, and in which the thiophanthraquinone radical or radicals and the anthraquinone radical may be unsubstituted or may contain simple monovalent substituents such as halogen, methoxy, benzoylamino and thenoylamino groups. In all cases the thiophanthraquinone radical is attached to the aminonitrogen atom through its benzene nucleus.

While a number of vat dyes in the yellow range have been used in the dyeing and printing of textiles, the fastness properties of these yellow colors are poor as compared with the fastness properties of many of the other colors in the vat dye class. Where yellow dyes in this class with improved fastness properties have been found, they in turn are either dull or weak tinctorially and therefore the various yellow dyes in the vat dye class are chosen to answer a particular need, balancing the question of fastness, brightness and cost of the particular dye available. In U. S. Patent 2,175,803, a group of imidazole and oxazole dyes containing an azo linkage are disclosed which dye vegetable fibers in yellowish shades and which are said to exhibit good fastness to chlorine and boiling soap solution, and, in certain cases, to light. It has been found, however, that these dyes are deficient in wet fastness particularly in kier boiling, and in their vat stability. In U. S. Patent 2,228,455 a series of dianthraquinonylimides containing azo groups are disclosed which have relatively good fastness properties but which have been found to dye in dull and considerably weaker shades than the azole types of the first mentioned patent.

It is an object of the present invention to produce new and valuable dyes and dye intermediates of the thiophanthraquinone series which dye cotton and related fibers from the usual alkaline hydrosulfite vats in desirable yellow shades and which exhibit improved brightness, tinctorial strength and fastness properties as compared to dyes of similar shade now available. It is a more specific object of the invention to produce thiophanthraquinone compound with one mol of 4,4- aZobiphenyll' ,4 -dicarbonylchloride to produce the azobiphenyl-4" carbonylaminothiophanthraquinonel' -carbonylchloride as more particularly disclosed in our co-pending application Serial No. 99,874 filed of even date herewith. These azobip-henyl-4' -carbonylaminothiophanthraquinone-4"'-carbonyl chlorides are further condensed with an aminothiophanthraquinone or an aminoanthraquinone. Where the same aminothiophanthraquinone is to be condensed on both carbonylchloride groups of the azobiphenyl compound; 2 mols oi the aminothiophanthraquinone may be condensed directly with the azobiphenyldicarbonylchloride. The condensations are preferably carried out in an inert organic solvent under anhydrous conditions at temperatures of from 140 to 200 C. The resulting dyes may be purified by recrystallization from concentrated sulfuric acid or by the usual bleaching with 2.1-

kaline hypochlorites in the manner customarily employed in purifying vat dyes of the anthraquinone vat dye series.

In the following examples, the azobiphenyldicarboxylic acid employed may be readily prepared by an alkaline dextrose reduction of 4,4'-nitrophenylbenzoic acid. The conversion of the dicarboxylic acid to the dicarboxylic acid chloride having a melting point of 262 C. may be efiected by reacting the sodium salt of the azobiphenyldicarboxylic acid with thionyl chloride or phosphorous pentachloride in an inert solvent such as nitrobenzene and in the presence of a catalyst such as pyridine.

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 '160" C. for four hours, filtered at C., and

the bright yellow crystalline product was washed ill gives an orange color in concentrated sulfuric acid and dyes vegetable fibers in bright yellow biphenyldicarbonyl chloride with 3.4 parts of aminothiophanthraquinone) was added 5 parts of 1-amino-5-benzoylaminoanthraquinone. The charge was heated at 160 C. for four and onehalf hours, filtered at 90 (3., and the product was washed with nitrobenzene, alcohol and O O H l ll water. The bright yellow 4,4'-azobiphenyl-4"- (5 carbonylaminothiophanthraquinone) 4' shades from an orange alkaline hydrosulfite vat. (1 carbonylamino 5 benzoylaminoanthra- Example 2 At 130 0., 2.5 parts of l-amino-G-chloroanquinone), which was purified by alkaline bleaching in the usual method, is represented by the formula:

thraquinone were added to a mixture of 6 It gives an orange color in concentrated sulfuric parts of ,4'-azobiphenyll"-(S-carbonylaminothiophanthraquinone) 4 carbonyl chloride and parts of nitrobenzene. The charge was treated in the same manner as that in Example 1. The greenish-yellow needle-like 4,4-azobiphenyl 4" (5 carbonylaminothiophanthraquinone) 4" (1 carbonylamino 6 chloroanthr'aquinone), which is represented by the formula:

acid and dyes vegetable fibers in bright yellow shades of excellent light fastness from an orange alkaline hydrosulfite vat.

Example 4 A mixture of 100 parts of dry nitrobenzene, 6.5 parts of azobiphenyldicarbonyl chloride and 6.9 parts of 5 aminothiophanthraquinone was gives an orange color in concentrated sulfuric acid and dyes vegetable fibers in bright yellow shades of excellent fastness properties from orange alkaline hydrosulfite vat.

Example 3 To a mixture of 100 parts of dry nitrobenzene di (5-carbonylaminothiophanthra quinone), which has the formula:

and 4,4 azobiphenyl 4" (5 carbonylaminothiophanthraquinone) 4" carbonyl chloride gives an orange color in concentrated sulfuric acid and dyes vegetable fibers in bright yellow (prepared by condensation of 6.5 parts of azoshades from an orange alkaline hydrosulfite vat.

Example 5 anthraquinone), which was purified through To a mixture of 75 parts of dry nitrobenzene bleaching by t usual m thods, is r p s d and 5 parts of azobiphenyldicarbonyl chloride at by the formula:

, (I) it me E 9, en U In 130 C., was added parts of G-amlnothio- It gives an orange solution in concentrated sulphanthraquinone. The charge was heated at r c ac d and y v a l fibers in bright 150 C. for one hour, at 160 C. for four hours, yellow shades from an orange alkaline y then filtered at 100 C., and the greenish-yellow u fite vat.

needle-like product was washed with nitro- Example 7 benzene, alcohol, water, and was dried. The To a slurry of 4,4-azobiphenyl-4"-(5 p y1 c y a bonylamino 8 benzoylaminothiophanthra ph nthraquinone), which was acid pasted and quinone)-4"'-carbony1 chloride in nitrobenzene bleached by usual methods, is represented by the (prepared by condensation of 6 parts of azobiformula: phenyldicarbonyl chloride with 4.8 parts of 5- cio oe nd in It gives an orange color in concentrated sulfuric benzoylamino 8 aminothiophanthraquinone in acid and dyes vegetable fibers in bright green- 90 parts of nitrobenzene) were added 4.7 parts yellow shades from an orange alkaline hydrcof 1-amino-4-benzoylaminoanthraquinone. The sulfite vat. This color is readily vattable and charge was heated at 160 C. for one hour, then tinctorially strong. It has good fastness to light at 190 C. for four hours, filtered at 100 0., and and to wet treatments. The corresponding the product was washed with nitrobenzene, -a1- molecule from two mols of Z-amino-anthraquim cohol, water and dried. The orange-colored one is almost unvattable and tinctorially about crystalline 4,4 azobiphenyl 4" (5- carbonylone-seventh as strong. amino 8 benzoylaminothiophanthraquinone) Exampze 6 4" (1 carbonylamino 4 benzoylami anthraquinone), which was acid pasted and A mixture of 75 parts of dry mtrobenze e, bleached by usual methods, is represented by 4,4 azobiphenyl 4 (5 carbonylamino-2- the formula:

ch roth p q y OhlO- It gives a red-orange solution in sulfuric acid d p epared in situ from 5 parts of azobiand dyes vegetable fibers in yellow-orange shades p yl i y acid and -3 P ts Of 2- from a brown-red alkaine hydrosulfite vat. chloro 5 aminothiophanthraquinone (disclosed in applications Serial Numbers 786,335 and 786,- Example 8 3'37 now U. S. Patents 2,480,109 and 2,480,111, t 130 C" 9 4 b n-, f llchlormgfimmm respectively) 1, and 2.8 parts of l-aminoanthraanthraqumone were added t a mixture of 4 4' quinone was heated at four and azobiphenyl -4"- (5-carbonylaminothiophanthrahalf The charge was filtered at quinone) -4"-carbonyl chloride (prepared from and the bright yellOW D Was Washed With 16 parts of azobiphenyldicarbonyl chloride and nitmbenzene, alcohol and Water- The 8.4 parts of 5-aminothiophanthraquinone) and biphenyl (5 carbonyl-amino 2 chloro" the charge was treated as that in Example 1.

thi pha t qu ca y a o- The greenish yellow crystalline 4,4'-azobiphenylwith an aminothiophanthraquinone compound in 2,559,372 7 4" carbonyl amionothiophanthration Serial No. 99,871] was heated one hour at quinone) 4 (2 carbonylamino 1 chloro- 130 (3., three hours at l85-190 C. and then one anthraquinone), which was purified through hour at 205-210 0., at which time evolution of bleaching, is represented by the formula: hydrogen chloride was complete. The greenish- It gives an orange solution in concentrated sulyellow crystalline compound, which is obtained furic acid and dyes vegetable fibers in yellow in excellent yield, has the structure:

shade of good tinctorial strength from an orange and dyes cotton greenish-yellow shades from an alkaline hydrosulfite vat. orange alkaline hydrosulfite vat.

Other products of this series, which were pre- Other combinations of the azobiphenyl-carpared by condensation of azobiphenylcarbonbonylaminothiophanthraquinone-carbonyl chlo ylaminothiophanthraquinonecarbonyl chlorides rides with aminothiophanthraquinones or aminowith aminothiophanthraquinones or aminoananthraquinones may be effected in the same manthraquinones by essentially the same method as her as illustrated in the above examples to give that described in Example 8, are described in the dyes having similar dyeing characteristics, such following table. In this table the aminothioas, for example, phanthraquinone employed in the preparation of the azobiphenylcarbonylaminothiophanthraqui- 4,4-azobiphenyl-4 (5- carbonylaminothiophnonecarbonyl chloride is illustrated in column R, anthraquinone) l"-carbonyl chloride with 5- while the amino compound which is to be conchloro-6-aminothiophanthraquinone, densed therewith is listed under R. 4,4 azobiphenyl-4"-(G-carbonylamino-B-chlo- Properties of Product Ex R R Appearance Golgzisnion. Calggof 9 i. 5-Amiuotl1iophanthraquinone l,3-dibr0mo-2-fln1in0anthral1uiuone- Green-yellow orange orange. 10 fi-Aminothiophanthraquinone l-chloroQaIninoG-nthraquinone Vgg gEi Sn-yelJQW do Do, 11 do Z-amino-3-bromoantl1raquinoxie Vgg g ree n-yellow do Do. 12 6-Amino-5-chlorothiophanthraquinone l-ch1oro-2 aininoanthraquinone "3 33}? do Do. 13 ido l-amino-5-benzoylaminoanthraquinone. Green-yellow do Do. 14 do 5-chlo1'o-6-aminothiophanthraquinone G fgg nyellow ndo D 15". 6-Amino-7-bromothiophanthraquinone 2-amino-3-bromoanthraquinone ve ri g i s an-yellow do Do. 160. 6-Amino-5,7-dibromothiophanthraquinone i 1,3-dibromo-2 ami11oanthra quinone v i y gi in-yellow .do Do. 1 I 8-Aminothiophanthraquinone l-chloro-2-aminoanthraquinone yfim g mis .410 Do. 18-.- fi-Aminothiophanthraquinone 1-amino4-benzoylaminoanthraquinone Orange plates red-mange". brown-red 19 7-aminothiophanthraquinone 1-chl0r0-2-amin0nnthraquinone virggcrglen-yellow orange orgg'e.

It will be obvious that, in place of the 4,4'- rothiophanthraquinone)-4"carbonyl chloride azobiphenyl 4" (5 carbonylaminothiophanwith Z-aminoanthraquinone,

thraquinone) Ar -carbonyl chloride used in the 4,4 azobiphenyl 4 (5 carbonylamino 3- above examples, the unsymmetrical substituted methoxythiophanthraqumone) m carbonyl azobiphenyldicarbonyl Chloride compound may chloride With 5-chloro-6-aminothiophanthrabe obtained by starting With the 4,4-azobiphenylqumone, and

interns?first:strains thiophanthraquinone) -41 carbonyl chloride the manner illustrated in the following example. with 1"chloro'z'ammoanthraqumone' Example 20 In place of the substantially pure aminothi0- A mixture of 15 parts of 6 ammothiophan phanthraquinones, it will be obvious that mixthraquinone, 80 parts of dry nitrobenzene and 4.7 tul'es may be usedmore Particularly the parts of 4,4' b1 1 4" (1- -g mally occurring mixtures of aminothiophanthrabonylamino 3 chloroanthraquinone) -4"'-carquinones or halogen-aminothiophanthraquinonesbonyl chloride [prepared as described in applicasuch as a mixture of the 5,8-aminothiophanthra quinones, the 6- and '7-aminothiophanthraquiin which at least one R stands for a thiophannones, the -chloro-6-amincor the 8-chlorothraquinone radical and the second R for a radi- 7-aminothiophanthraquinones. cal of the group consisting of thiophanthraqui- Symmetrical diamides may be prepared by none radicals and anthraquinone radicals, the densation of two niols of an aminothiophanthra- 5 ihioohanthraquilwne d the quin quinone with one mol of azobiphenyldicarbonyl Tactical-S in each case bemg of W group chloride. Condensation may be carried out under Sistmg of the ,unSubwtU-ted tiflophanthlaqul a wide variety of conditions as to temperature F r anfhraqulmne adlcals and the and time depending upon the reactants to be thlophanthraqumone and anthraqumone radicals 10 which carry monovalent substituents of the group consisting of chlorine, bromine, methoxy, benzoylamino and thenoylamino groups, which substituents in the case of the thiophanthraquinone radical are attached to the benzene nucleus and the thiophanthraquinone radical is attached to the amino-nitrogen atom of the carbonylamino group used. A temperature range of 140-200 C. usually afiords most satisfactory results although temperatures outside of this range are occasionally necessary. The condensations are carried out in inert organic solvents such as the aromatic hydrocarbons and chlorinated and nitrated aromatic hydrocarbons, and catalySts Such as pyl in the formula through its benzene nucleus. dine may be used if desired. 2. The azobiphenylcarbonylaminothiophan- The compounds of this invention are new and thraquinones of the formula:

useful vat dyestuffs, dyeing generally in the yellow in which the thiophanthraquinone radical shown shade range, having very good light fastness. is attached to the amino-nitrogen atom through They are particularly valuable in that they are its benzene nucleus, R stands for a radical of ood pr t g colors as well as dy ng colo s, the group consisting of anthraquinone and thiobuilding up to stronger shades than can be 010- phanthraquinone radicals the thiophanthraquitained with the corresponding anthraquinone none radical being attached to the amino-nitrocolors. Of the new compounds, of particular gen atom through its benzene nucleus, and X and utility are those with a halogen ortho to the Y which are ortho to the amino-nitrogen atoms amino groups which on further reaction can be stands for members of the group consisting of ring-closed to an oxazole or a thiazole compound. hydrogen, chlorine and bromine atoms and at The dyes thus formed have better tinctorial least one thereof stands for one of the halogen strength and fastness properties than the correatoms.

sponding anthraquinone compound. The o p y c rbo ylaminothiophan- The various intermediates employed in the thraquinone of the formula:

0 no co -tho preparation of the compounds of this invention 4. The azobiphenylcarbonylaminothiophanmay be produced by the processes more particuthraquinone of the formula:

0 o I i 0 r r 1 Ni '-OO N=N O-N 3 s larly described in our co-pending application 5. The azobiphenylcarbonylaminothiophan- Serial No. 99,874, filed of even date herewith. thraquinone of the formula:

HERMAN E. SCI-IROEDER.

We claim: LORRAINE A. RINGROSE. 1. The azobiphenylcarbonylaminothiophanthraquinones of the general formula: No references cited. 

1. THE AZOBIPHENYLCARBONYLAMINOTHIOPHANTHRAQUINONES OF THE GENERAL FORMULA: 